Nonvolatile memory device using semiconductor nanocrystals and method forming same

ABSTRACT

A method of making a nanoparticle array that includes replicating a dimension of a self-assembled film into a dielectric film, to form a porous dielectric film, conformally depositing a material over said porous dielectric film, and anisotropically and selectively etching said deposited material.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a divisional application of application Ser.No. 11/373,127 filed on Mar. 13, 2006 now U.S. Pat. No. 7,985,686, whichis a divisional application of application Ser. No. 10/465,797 filed onJun. 20, 2003 now U.S. Pat. No. 7,045,851.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention generally relates to a memory device, and moreparticularly to a nonvolatile memory device using semiconductor crystalsand a method for making the same.

2. Description of the Related Art

Nonvolatile memory is ubiquitous in today's technology-laden world, andthe most prevalent type of device used to store information is the flashmemory.

In addition to the need for integrated nonvolatile memory in logicsystems, there is a large (and rapidly increasing) market for flashmemories as stand-alone storage elements. Cellular telephones anddigital cameras are several examples of devices which benefit fromnonvolatile flash memory cards.

There are various forecasts predicting increased future markets for thistype of storage (e.g., see P. Pavan, R. Bez, P. Olivio, and E. Zanoni,IEEE Proc. 85 1248 (1997).

Flash memory is based on the concept of a field effect transistor (FET)whose threshold voltage (VT) can be reversibly changed between first andsecond values.

As shown in the side sectional view of FIG. 1( a), a conventional flashmemory device 100 is shown including a substrate 101, source 102 anddrain 103, formed in the substrate 101 with a channel 104 formedtherebetween, a program oxide 105 formed over the substrate 101, afloating gate 106 formed over the program oxide 105, a control oxide 107formed over the floating gate 106, and a control gate 108 formed overthe control oxide 107.

A main component of the flash memory device 100 which facilitates thismulti-state operation is a conducting floating gate 106 in the gatestack of the transistor (see FIG. 1( a)) which is coupled to itssurroundings (the control gate 108, and also the channel 104/source102/drain 103 regions) via dielectrics (e.g., 107, 105) on top andbelow.

The device 100 is programmed by injecting charge into the floating gate106 (though the program oxide 105), and is erased by expelling chargefrom the floating gate 106. These devices 100 are made nonvolatile by 3decoupling the floating gate 106 from the source 102/drain 103/channel104 and control gate 108 with a sufficiently thick control oxide 107.

As with all other semiconductor technologies, flash memory continues toscale to increasingly higher densities. At the same time, improvementsin device speed, power consumption, and endurance (e.g., number of timesthe memory can be read/erased before failing) also pay obvious benefits.

Finally, some flash memory devices have improved performance throughstorage of multiple bits per memory cell (e.g., most notably Intel'sStrataFlash™ technology currently stores 2 bits/cell with announcedfuture plans to increase the number of bits/cell). This is achieved byprogramming the floating gate 106 with different amounts of charge inorder to achieve multiple possible threshold voltage (VT) shifts in thesame device.

The pathway to many of these density and performance benefits involvesscaling the memory FET, which is becoming increasingly difficult. Forexample, shrinking the device width in order to improve packing densityand speed results in increased drain turn-on effects from capacitivecoupling between the drain 103 and the floating gate 106.

Also, thinning the program oxide 105 thickness in order to achieve lowerwrite/erase voltages (and thus lower power) has the effect of reducingretention times and reliability.

Referring to FIG. 1( b), nanocrystal memory devices have been proposedas a way to improve the scaling of flash memory devices, and also as apossible means to achieve robust multi-bit operation (e.g., see H.Hanafi, IEEE Trans. Elect. Dev. 43 1553 (1996); S. Tiwari, F. Rana, H.Hanafi, A. 4 Hartstein, E. Crabbe, C. Chan, Appl. Phys. Lett. 68 1377(1996); and S. Tiwari, F. Rana, K. Chan, H. Hanafi, W. Chan, D.Buchanan, IEDM 521 (1995)).

Turning to the conventional nanocrystal memory device 150 shown in FIG.1( b), the structure is somewhat similar to that shown in FIG. 1( a)except that the floating gate 106 is replaced with nanocrystals 156.

That is, a basic idea in nanocrystal memory devices is that breaking upa continuous, conducting floating gate 106 into small bits of isolatedconducting material can aid in overcoming some of the roadblocks tofurther scaling.

The nanocrystal floating gate 156 has reduced capacitive coupling to thesource 151/drain region 152, which leads to a smaller drain turn-oneffect. In addition, the nanocrystal floating gate 106 should make thedevice less susceptible to stress-induced leakage current. That is, ifan individual nanocrystal becomes shorted to the channel 154, othernanocrystals remain unaffected. In a standard floating gate device(e.g., such as device 100), any short to the channel 104 is disastrousbecause charge can no longer be maintained in the floating gate 106.

Nanocrystal floating gate devices (e.g., such as those exemplified byreference numeral 150 in FIG. 1( b)) have improved retentioncharacteristics compared to conventional flash devices with the sameprogram oxide thicknesses, because most charge leakage from the floatinggate 156 occurs to the heavily doped source 152/drain regions 153.

In a flash device, such leakage will deplete charge from the entirefloating gate, resulting in a loss of memory (e.g., in the same way asstress-induced leakage currents compromise the device).

In a nanocrystal device, only those nanocrystals in close proximity tothe source 152/drain 153 lose their charge by this leakage mechanism,while those farther away (e.g., near the device center) do not. Thisargument assumes that there is no electrical conduction betweennanocrystals in the floating gate 156 (e.g., a condition which can becontrolled via the nanocrystal density).

The improved retention properties of nanocrystal floating gate devices150 allows scaling to thinner program oxides 155, which can result inadded benefits. Thinner oxides 155 permit programming at lower voltagesusing direct quantum mechanical tunneling, rather than Fowler-Nordheimfield emission processes.

In addition to the obvious lower-power benefit of lower voltageoperation, there is some evidence which suggests that a direct tunnelingwrite/erase mechanism puts less stress on the program oxide 155, therebyresulting in increased device cyclability. Modeling also suggests thatdevices with thinner oxides 155 can be programmed more quickly (e.g.,see M. She, Y. C. King, T. J. King, C. Hu, IEEE Device ResearchConference, 139 (2001)).

One of the more intriguing aspects of nanocrystal memories 150 is thepossibility to program the floating gate 156 with discrete numbers ofelectrons, which in turn leads to multiple discrete, well-defined device6 threshold voltage (VT) shifts. The idea is that the electrostaticenergy necessary to add a single charge to a sufficiently smallnanocrystal can become significant. This electrostatic charging energyis given by:

$\begin{matrix}{U = \frac{{\mathbb{e}}^{2}}{2\; C_{\Sigma}}} & (1)\end{matrix}$where e is the electron charge and C_(Σ) is the nanocrystal capacitanceto its surroundings. Tiwari et al. have estimated this charging energyfor different diameter nanocrystals (in this calculation, thenanocrystals were assumed to be spherical) (e.g., see S. Tiwari, J. A.Wahl, H. Silva, F. Rana, J. J. Welser, Appl. Phys. A 71 403 (2000)). Theresults are shown in Table 1. The charge stored in the floating gatewill shift the device VT by an amount:

$\begin{matrix}{{\Delta\; V_{T}} \approx \frac{- Q}{C_{ctl}}} & (2)\end{matrix}$where Q is the amount of charge stored on the floating gate 156 and Cctlis the floating gate capacitance to the control gate 158. Tiwari et al.have also computed the ΔVT for charge stored in different sizednanocrystals. These results are also shown in Table 1 below.

TABLE 1 Nanocrystal ΔVT (for a single Diameter (nm) Ec (eV) addedcharge) (V) 30 .011 .03 20 .018 .06 10 .036 .23 5 .072 .8 2 .178 >5

Table 1 above illustrates a calculated charging energy (Ec) andcorresponding threshold voltage shift (ΔVT) for nanocrystals ofdifferent sizes (e.g., from Tiwari et al., mentioned above).

Table 1 shows that the addition of a single charge to a nanocrystal canresult in a significant threshold voltage shift (ΔVT˜0.5 V for ananocrystal diameter between 5-10 nm). In this way, it may be possibleto use this effect for multi-bit storage, where discrete VT shiftscorrespond to adding incrementally larger numbers of charges to thefloating gate 156. These types of discrete VT shifts from adding singlecharges have been seen experimentally in extremely small devices inwhich the floating gate 156 contains only a single nanocrystal (e.g.,see J. J. Welser, S. Tiwari, S. Rishton, K. Y. Lee, Y. Lee, IEEE Elect.Dev. Lett. 18 278 (1997).

In more conventional devices where the floating gate 156 contains manynanocrystals (e.g., instead of a single one), effects due to discretecharging are usually averaged out due to nanocrystal size distributions.

In order to observe this effect (and thus make possible multi-bitstorage in the device), it is essential to define all nanocrystals to beof similar size.

Several groups have demonstrated implementations of nanocrystal-basedflash memories. However, none has defined all nanocrystals to be ofsimilar size by using a self-assembly technique. Tiwari et al. havepublished numerous papers and also hold a patent (e.g., see U.S. Pat.No. 5,714,766, incorporated herein by reference) on a memory devicebased on CVD-deposited silicon nanocrystals.

Kim et al. have also published results on a similar device (e.g., see I.Kim et al., IEEE Electon Dev. Lett. 20 630 (1999)). Welser et al. (e.g.,see above-mentioned J. J. Welser, S. Tiwari, S. Rishton, K. Y. Lee, Y.Lee, IEEE Elect. Dev. Lett. 18 278 (1997), have demonstrated a memorydevice based on a single nanocrystal in the floating gate. This type ofdevice is often called a “quantum dot memory”. Chou et al. also hold apatent on this device structure (e.g., see U.S. Pat. No. 6,069,380,incorporated herein by reference).

Ostraat et al. have described operation of a memory device in which thefloating gate contains aerosol-deposited silicon nanocrystals (e.g., seeM. L. Ostraat et al., Appl. Phys. Lett. 79 433 (2001)).

Finally, King et al. have described a device containing germaniumnanocrystals (e.g., see Y. C. King, T. J. King, C. Hu, IEDM, 155(1998)).

However, in each of these conventional demonstrations, the nanocrystalsizes were not well-defined, thereby leading to limitations on deviceperformance improvements.

Additionally, as mentioned above and prior to the present invention,nanocrystal floating gate memories have been difficult to use formulti-bit memory applications, because of the large nanocrystal sizedistributions.

Further, prior to the present invention, defining all nanocrystals to beof substantially similar size (and thus making possible multi-bitstorage in the device), has not been achieved.

Moreover, there has been no technique which produces a nanocrystalmemory device having nanocrystal size distributions which aresubstantially uniform, using a self-assembly technique.

In sum, the conventional techniques (and subsequently the resultingstructure) to make a nanocrystal memory have been notoriouslyunreliable, and it has been difficult to obtain uniform size of thenanocrystals, and difficult to control the spacing of the distributionaround the sample, each of which impact the performance of the device.

SUMMARY OF THE INVENTION

In view of the foregoing and other problems, drawbacks, anddisadvantages of the conventional methods and structures, an exemplaryfeature of the present invention is to provide a method (and structure)for building a nanocrystal memory device.

Another exemplary feature of the present invention is to form ananocrystal memory device in which a self-assembled material is used totemplate or define the nanocrystals, and allowing good control over theuniformity of the size of the nanocrystal particles, and over theirdistribution (e.g., where the nanocrystals are located and the spacingbetween them).

In a first exemplary aspect of the present invention, a floating gatefor a field effect transistor, includes discrete nanoparticles whosedimensions and distribution are defined by a self-assembling material.For example, in one explemplary aspect, the nanoparticles may havediameters between about 2 and about 30 nanometers, with sizedistributions no greater than substantially 15% of a mean diameter ofthe nanoparticles.

In a second exemplary aspect of the present invention, a field effecttransistor, includes a source region and a drain region formed in asemiconductor material, a channel region disposed between the sourceregion and the drain region, an insulating layer of electricallyinsulating material disposed over the channel region, a floating gatelayer of electrically conducting material disposed over the insulatinglayer, a layer of electrically insulating material disposed over thefloating gate layer, and a gate electrode overlying the layer ofinsulating material. The floating gate layer includes discretenanoparticles whose dimensions and distribution are defined by aself-assembling material.

For example, in one exemplary aspect, the nanoparticle density may begreater than 10¹⁰/cm². In addition, in one exemplary aspect, thenanoparticles may be arranged in a cubic lattice, or a close-packed,two-dimensional hexagonal lattice. Further, the hexagonal lattice mayinclude an average inter-nanoparticle distance between about 1 and about2 times an average nanoparticle diameter, and a standard deviation ofinter-nanoparticle distance no greater than substantially 20% of themean distance. More specifically, the nanoparticles in the floating gatemay include first and second distinct sizes, each with diameter standarddeviations being less than approximately 15% of a mean diameter of thenanoparticles.

Further, in this exemplary aspect of the present invention, selfassembly may involve a block copolymer film. For example, the blockcopolymer may include a diblock copolymer including a molecular weightwithin a range of about 5,000 kg/mol to about 250,000 kg/mol.

In a third exemplary aspect of the present invention, a method offorming a floating gate for a field effect transistor, includes formingdiscrete nanoparticles whose dimensions and distribution are definedusing a self-assembled material to template the nanoparticles.

In a fourth exemplary aspect of the present invention, a method formaking a uniform nanoparticle array, includes replicating a dimension ofa polymer template in a dielectric film, to form a porous dielectricfilm, conformally depositing a material over the porous dielectric film,and anisotropically and selectively etching the deposited material.

In a fifth exemplary aspect of the present invention, a method formaking a uniform nanoparticle array, includes performing a diblockcopolymer thin film self assembly over a material film, creating apolymer dot array from the diblock copolymer thin film, and using apolymer dot of the polymer dot array as an etch mask for a nanoparticlereactive ion etching (RIE) of the material film.

In a sixth exemplary aspect of the present invention, a method formaking a uniform nanoparticle array, includes performing a diblockcopolymer thin film self assembly over silicon, creating a porouspolymer film, directionally depositing a first material over the porouspolymer film, and dissolving the polymer to lift off at least one regionof the first material deposited over the porous polymer.

In a seventh exemplary aspect of the present invention, a method formaking a uniform nanoparticle array, includes performing a diblockcopolymer thin film self assembly over a first dielectric over anoxidizable material film, creating a porous polymer film, transferring apattern into the first dielectric, etching the pattern into thematerial, and thermally oxidizing the material until a narrowestmaterial region between hexagonally-arranged pores close, therebyleaving an array of material nanoparticles.

In an eighth exemplary aspect of the present invention, a method formaking a uniform nanoparticle array, includes performing diblockcopolymer thin film self assembly over a first dielectric on silicon,creating a porous polymer film, transferring a pattern into the firstdielectric, and selectively growing epitaxial silicon off a siliconsubstrate from within pores to create a silicon nanoparticle array.

Additionally, the invention provides a method of fabricating ananocrystal memory device.

With the unique and unobvious combination of exemplary features of theinvention, a nanocrystal memory device can be formed in which thenanocrystals can be defined using a self-assembly process.

Further, the nanocrystal memory device (and the method for forming it)allows good control over the uniformity of the size of the nanocrystalparticles, and over their distribution (e.g., where the nanocrystals arelocated and the spacing between them).

Hence, the inventive method results in a device having a regular arrayof such nanocrystals throughout the active area of the device.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing and other purposes, aspects and advantages will be betterunderstood from the following detailed description of an exemplaryembodiment of the invention with reference to the drawings, in which:

FIG. 1( a) illustrates a schematic diagram of a conventional flashmemory device 100;

FIG. 1( b) illustrates a schematic diagram of a conventional nanocrystalmemory device 150;

FIG. 2( a) illustrates a top-down scanning electron micrograph (SEM)image of a porous polystyrene (PS) thin film on silicon formed bydiblock copolymer self assembly, and in which hexagonally-arranged darkcircles are cylindrical holes in the PS film down to the substrate fromwhich the PMMA has been selectively removed;

FIG. 2( b) illustrates a histogram of pore diameters showing a narrowdistribution of ˜10% centered around 20 nm for PS-PMMA molecular weight67 kg/mol;

FIGS. 3( a)-3(h) illustrate schematic diagrams depicting siliconnanocrystal array formation based on diblock copolymer self assembly,and more specifically:

FIG. 3( a) illustrates a step 310 of assembling PS-PMMA diblockcopolymer on a thermally-oxidized silicon substrate;

FIG. 3( b) illustrates a step 320 of removing the PMMA block, leaving aporous PS template;

FIG. 3( c) illustrates a step 330 of using reactive ion etching (RIE) totransfer the PS pattern into the oxide film;

FIG. 3( d) illustrates a step 340 of stripping the remaining polymer,leaving a porous oxide film;

FIG. 3( e) illustrates a step 350 of conformally depositing a material(e.g., silicon);

FIG. 3( f) illustrates a step 360 of anisotropically etching thesilicon; and

FIG. 3( g) illustrates a step of 370 stripping oxide to leave thesilicon nanocrystal array on silicon; and

FIG. 3( h) illustrates a flowchart of the method 300 shown in FIGS. 3(a)-3(g); and

FIGS. 4( a)-4(j) illustrate a schematic process flow 400 showingformation of a nanocrystal memory device, and more specifically:

FIG. 4( a) illustrates a step of assembling PS-PMMA diblock copolymer ona thermally-oxidized silicon substrate;

FIG. 4( b) illustrates a step of removing the PMMA block, leaving aporous PS template;

FIG. 4( c) illustrates a step 430 using reactive ion etching (RIE) totransfer the PS pattern into the oxide film;

FIG. 4( d) illustrates a step of stripping the remaining polymer,leaving a porous oxide film;

FIG. 4( e) illustrates a step of conformally depositing a material(e.g., silicon);

FIG. 4( f) illustrates a step of anisotropically etching the silicon;

FIG. 4 (g) illustrates a step of stripping oxide to leave siliconnanocrystal array on silicon;

FIG. 4 (h) illustrates a step of stripping oxide to leave siliconnanocrystal array on silicon;

FIG. 4 (i) illustrates a step of stripping oxide to leave siliconnanocrystal array on silicon; and

FIG. 4( j) illustrates a flowchart of the method 400 shown in FIGS. 4(a)-4(i).

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS OF THE INVENTION

Referring now to the drawings, and more particularly to FIGS. 2-4( j),there are shown exemplary embodiments of the method and structuresaccording to the present invention.

Exemplary Embodiment

First, hereinbelow is described an exemplary method for making densesilicon nanocrystal arrays based on self-assembly according to thepresent invention.

It is noted that, while a diblock copolymer is described exemplarilybelow, the invention is not limited to such materials as would be knownby one of ordinary skill in the art, taking the present invention as awhole.

That is, the invention can generally take advantage of self-assemblingmaterials which are not exclusively the particular diblock copolymersdescribed below. There are a variety of different material whichnaturally form regular arrays, thereby allowing the invention to takeadvantage of the scale in self-assembling materials. Indeed, there arenanoparticles which self-assemble, there are proteins which naturallyself-assemble, there are block copolymers which naturally self-assemble,there are self-assembled pores in anodized alumina, there are otherself-assembling molecules including self-assembled monolayers (SAMs),etc., all of which the invention may be applied advantageously thereto.

The invention's use of self-assembly is clearly different from theconventional techniques. That is, the conventional techniques mayinclude using a chemical vapor deposition (CVD) technique to scattersilicon over the sample. While this technique may be somewhat acceptableunder some conditions, there is little control of the distribution, andthere are small and large sizes randomly over the sample.

Another technique (e.g., on the other extreme from CVD) is usinglithography in which patterning occurs, and more specifically a point iswritten at each location where a particle is to be placed. Such atechnique is very tedious and slow, is not a very manufacturablesolution, and does not achieve the resolution or reliability that can beachieved in a self-assembly process.

Thus, the invention's use of self-assembly overcomes the problems of theconventional techniques and allows controlling the size distribution and17 positions (e.g., situs) of the particles, as well as a techniquewhich is potentially more manufacturable, simpler, and scalable.

In order to achieve the above-mentioned performance improvements overthe conventional flash memory and conventional nanocrystal memorydevices, the present inventors have discovered that nanocrystals in thedevice floating gate according to the present invention must be discrete(i.e., electrically isolated from each other), and densely-spaced (e.g.,in order to prevent electron conduction by percolation through thesilicon channel).

For multi-bit memory operation, nanocrystal sizes should be highlyuniform. Nanocrystal sizes on the order of about 3 nm to about 10 nmdiameters should provide sufficient Coulomb charging energies forsingle-electron charging behavior at room temperature (e.g., seeabove-mentioned Tiwari et al. article).

Because the transistor device dimensions are typically defined at thelimit of lithographic resolution, the nanocrystals residing in the gatestack must be much smaller than this and therefore must be defined usingsome non-lithographic means.

As mentioned above, previous demonstrations have used CVD-deposited oraerosol-deposited nanocrystals, which have inherent size variations.

In the present invention, the nanocrystals are preferably patternedusing a self-assembly process, which sets (e.g., templates or defines)the dimensions, density, and uniformity of the nanocrystals. Thecharacteristic dimensions of self-assembled films depend on fundamentallength scales (e.g., 18 such as molecular size), and are thereforeinherently more controllable than structures defined using depositionprocesses, whose size distributions are limited by nucleation anddiffusion effects, and sample topography.

There are many self-assembling systems that result in regular arrays ofnanometer-scale features.

In the present invention, a system is provided based exemplarily ondiblock copolymer self-assembly in one embodiment. Obviously, theinvention is not limited to the diblock copolymer material as mentionedabove and would be clearly evident to one of ordinary skill in the arttaking the present application as a whole. Indeed, other materials whichcould be used may include, as mentioned above, self-assemblednanoparticles, anodized alumina, self-assembling proteins, etc.

Under suitable process conditions (e.g., such as molecular weight, blockweight ratio, film thickness, annealing conditions, surface treatmentand the like), diblock copolymer molecules can microphase separate on ananometer-scale length scale, thereby forming a hexagonal array of poresin a thin polymer film. Many different polymers (e.g., such as

-   -   Polybutadiene-polybutylmethcrylate,    -   Polybutadiene-polydimethylsiloxane,    -   polybutadiene-polymethylmethacrylate,    -   polybutadiene-polyvinylpyridine,    -   polyisoprene-polymethylmethacrylate,    -   polyisoprene-polyvinylpyridine,    -   polybutylacrylate-polymethylmethacrylate,    -   polybutylacrylate-polyvinylpyridine,    -   polyhexylacrylate-polyvinylpyridine,    -   polyisobutylene-polybutylmethacrylate,    -   polyisobutylene-polydimethoxysiloxane,    -   polyisobutylene-polymethylmethacrylate,    -   polyisobutylene-polyvinylpyridine,    -   polybutylmethacrylate-polybutylacrylate,    -   polybutylmethacrylate-polyvinylpyridine,    -   polyethylene-polymethylmethacrylate,    -   polymethylmathacrylate-polybutylacrylate,    -   polymethylmethacrylate-polybutylmethacrylate,    -   polystyrene-polybutadiene,    -   polystyrene-polybutylacrylate,    -   polystyrene-polybutylmethacrylate,    -   polystyrene-polybutylstyrene,    -   polystyrene-polydimethoxysiloxane,    -   polystyrene-polyisoprene,    -   polystyrene-polymethylmethacrylate,    -   polystyrene-polyvinylpyridine,    -   polyethylene-polyvinylpyridine,    -   polyvinylpyridine-polymethylmethacrylate,    -   polyethyleneoxide-polyisoprene,    -   polyethyleneoxide-polybutadiene,    -   polyethyleleoxide-polystyrene, and    -   polyetheleneoxide-polymethylmethacrylate        could be used for this process and other phase morphologies are        achievable (e.g., besides the hexagonal close-packed cylindrical        phase morphology described here). For example, other phase        morphologies may include spherical phase, the lamellar phase,        etc.

Hereinbelow and referring first to FIGS. 2( a) and 2(b), is detailed anexemplary self-assembly process using diblock copolymers exemplarilyincluding polystyrene (PS) and poly(methyl methacrylate) (PMMA).

First, the PS-PMMA diblock copolymers are preferably diluted in asolvent such as toluene or the like, and spin-cast as a thin filmpreferably having a thickness within a range of about a few nanometersto about a few hundred nanometers onto a sample (e.g., such as a hardmask oxide underneath (e.g., SiO2 which is thermally grown on silicon)or the like).

Then, the sample is heated (e.g., to a temperature within a range of140° C. to about 200° C., for several hours), thereby to promote themicrophase separation (hexagonally close packed (hcp)) array of theexemplary polymers (as shown exemplarily in FIG. 2( a)), which resultsin an ordered array formation in the film.

It is noted that it is the temperature which allows the two types ofpolymers to separate themselves from one another, and gives themmobility. Thus, the temperature and the time are significant, but mayvary depending upon the polymer system, with a particular thickness,concentration, etc.

For PS-PMMA copolymers having, for example, a molecular weight 67 kg/moland a mass ratio of 70:30 PS:PMMA, the resulting self assembled film(˜40 nm thick) is composed of 20-nm-diameter PMMA cylinders (e.g., theblack circles shown in FIG. 2( a)) arranged in a hexagonal lattice (40nm center-to-center spacing) embedded in a matrix of PS (e.g., shown inthe white areas in FIG. 2( a) around the PMMA). Again, the temperatureallows this material to phase-separate into the shown ordered pattern.Prior to being heated, the film is a mixture of the two polymers whichare not physically separated yet.

Again, it is noted that other morphologies can be employed, and thus“ordered array” for purposes of the present invention is certainly notlimited to hcp, and may include others such as spherical or lamellararrays which result in a different packing arrangement and which dependon the morphology of the materials and the ratio of molecular weights ofthe two polymers.

Then, a simple aqueous developing step (e.g., using acetic acid or thelike) can selectively remove the PMMA, leaving a porous PS film (e.g.,porous template having a thickness of 40 nm center-to-center spacing ofadjacent holes), as shown in FIG. 2( a).

The size and density of the holes created in the PS will be varieddepending upon the molecular weights of the materials (e.g., polymers)selected. Thus, choosing a material (e.g., PMMA) with a larger molecularweight will create larger holes (e.g., larger spacings). Greater (orlesser) spacing may be desirable depending upon the application. Forexample, for a flash memory device, it may be desirable to scale thedevices to a smaller physical size, and thereby scaling the size of thenanoparticles at the same time would be desirable. Selectively using themolecular weight of the materials allows such a scaling and control to asmaller size.

It is noted that, instead of the aqueous developing step, another stepcould be performed such as etching to leave the topography. Thus, theinvention is not limited to the aqueous developing step.

Returning to FIG. 2( a), the black circles indicate where the PMMAresides after it is phase-separated, and the white surrounding the PMMArepresents the PS matrix.

FIG. 2( b) shows a histogram of pore diameters in the PS-PMMA film. Thenarrow distribution (e.g., 10%) around the 20-nm mean-diameter showsthat these films are highly uniform. 22

The characteristic dimensions of features in the self-assembled film canbe adjusted by beginning with a different copolymer molecular weight,with typical pore diameters ranging from about 10 to about 100 nm.

Hence, FIG. 2( a) shows a top-down SEM image of a porous PS thin film onsilicon formed by diblock copolymer self assembly. Thehexagonally-arranged dark circles are cylindrical holes in the PS filmdown to the substrate from which the PMMA has been selectively removed.FIG. 2( b) shows a histogram of pore diameters showing a narrowdistribution of ˜10% centered around 20 nm for PS-PMMA molecular weight67 kg/mol.

The thin porous polymer template formed from diblock copolymer selfassembly is compatible with standard semiconductor processes (e.g., itdoes not introduce contamination and can be used in a manner similar toa polymer resist for reactive ion etch (RIE) transfer, etc.), and cantherefore be used as a mask for transfer of the nanometer-scale patterninto an underlying film or substrate (as described below). (This isoften desirable since the polymer template is neither thermally stablenor mechanically robust.)

The above steps will be used in building an exemplary device of interestaccording to the present invention, and as described below.

Exemplary Method of the Present Invention

FIGS. 3( a)-3(g) illustrate schematic diagrams depicting a method 300(see FIG. 3( h) showing a flowchart of the process) of siliconnanocrystal array formation based on diblock copolymer self assembly.That is, FIGS. 23 3(a)-3(g) illustrate schematically how to form a densearray of nanocrystals beginning with a self-assembled PS-PMMA film(e.g., which has been exemplarily formed as described above and shown inFIG. 2( a)).

First, the thin film of PS 303 and PMMA 304 is prepared on a thermallyoxidized (e.g., SiO2 or the like 302) silicon wafer 301, as shown inFIG. 3( a) (step 310 in FIG. 3( h)).

Then, the PMMA 304 is removed from the pores (e.g., as shown in FIG. 3(b) and in step 320), and the pattern (e.g., PS 303) is transferred intothe oxide film using a reactive ion etch (RIE) process (e.g., adirectional etch using CHF3 and argon or the like as shown in FIG. 3( c)and in step 330).

Then, the remaining polymer (PS) 303 is removed (e.g., as shown in FIG.3( d) and step 340), to leave a porous oxide film 302 which has the samedimensions as were in the porous polymer film.

In step 350 and as shown in FIG. 3( e), a thin film 306 ofconformally-deposited material (e.g., silicon, such as polysilicon oramorphous silicon, or potentially other materials from whichnanocrystals may be formed such as germanium or silicon germanium ormetal; an amorphous silicon layer will be assumed in the exemplaryprocess) is deposited on top of the porous oxide 302. The conformallydeposited film 306 preferably should be continuous and preferably shouldfully conformally cover the surface. Preferably, the thin film 306 has athickness which is more than about half the pore diameter because theholes must be filled up.

That is, since the thin film 306 should be a truly conformal depositionwhich covers every surface with the same thickness regardless of thesurface being a vertical surface or a horizontal surface, in order tofill up or “pinch off” the holes, the thickness deposited should be atleast half of the width on either side of the hole in order to pinchtogether. Thus, the thickness deposited should be at least half of thediameter of the pore.

Hence, since a directional etch is to be performed subsequently, it isnoted that because of the dimension of the patterns, a verticalthickness of the deposited silicon layer (e.g., amorphous silicon layer)is much greater inside the hole than it is on top of the oxide. Theinvention takes advantage of such a greater thickness to leave materialin these holes which will become the silicon nanocrystals.

Then, in step 360 and as shown in FIG. 3( f), the conformally depositedsilicon 306 is etched using an anisotropic directional etch RIE processthat leaves silicon 306 in the pores. Thus, the directional etch ofsilicon is performed (e.g., preferably selective against the siliconoxide, but not an etch stop in the conventional sense), stopping on thesilicon oxide. However, as mentioned above, it is not a natural stop,and it could be possible to continue to etch and remove all of thesilicon in the pores. However, this would not be desirable.

Thus, care must be taken to etch just a sufficient enough material, suchthat the silicon remains as discrete particles. Thus, the inventionensures that the amount of material left in the holes preserves thedimensions of the original polymer film (e.g., no shrinkage or growingthereof).

As shown in step 370 and in FIG. 3( g), optionally, the oxide 302 isselectively removed using a wet chemical etch or the like such as dilutehydrofluoric acid (HF), thereby resulting in a dense regular array ofsilicon “dots” (e.g., structures) extending over the sample thatreproduce the pore pattern in the original PS-PMMA film.

Thus, with the exemplary process above, the invention can form an arrayof silicon particles having the same dimensions as the polymer pores.

It is noted that, as further described below with regard to FIGS. 4(a)-4(g), the oxide 302 may be left in building a nanocrystal memorydevice using the present invention.

Several related and similar techniques could be implemented to createnanocrystal arrays, such as variations on the etch processes ordielectric films used. For example, the dielectric films do notnecessarily need to be SiO2. Such dielectric films could be oxide,nitride, high-k, or dielectric film stacks. Also, nanocrystals ofdifferent material, such as germanium, silicon germanium, and metal, canbe created by conformal deposition of materials other than silicon, suchas germanium, silicon germanium, and/or metal (e.g., different from thatof silicon shown in FIG. 3( e)).

Thus, with the exemplary process of the present invention, nanoparticles(e.g., formed of silicon or the like) have been formed having uniformdimensions by self-assembly.

Exemplary Process Flow for Nanocrystal Flash Memory Fabrication

Hereinbelow, a process flow is described for fabricating the nanocrystalflash memory device, as depicted in FIGS. 4( a)-4(i) and the flowchartof FIG. 4( j), utilizing the nanoparticles having the uniform dimensionsas described above.

A key advantage of this device structure is that self-assembly is usedto define a dense array of uniform nanometer-scale silicon nanocrystalsin the gate stack of the FET.

Gate Stack Formation:

A key component of the device is a gate stack, and hereinbelow isprovided a process flow for producing a stack containing uniformly-sizedsilicon nanocrystals separated from the silicon channel below by a thinprogram dielectric.

In step 410, a substrate 401 is provided (e.g., a p-type Si substrate).

Then, a layer of oxide 402 (e.g., exemplarily SiO2 is used, but ofcourse other oxides and nitrides or stack dielectrics or high kdielectrics could be employed is thermally grown on the substrate 401 ordeposited by CVD or atomic layer deposition (ALD) or other means, asshown in step 420 and FIG. 4( b). This layer thickness definesnanocrystal heights, and may exemplarily be between about 2 to about 20nm thick. As would be evident to one of ordinary skill in the art, theconductivity of the substrate could be different and the invention doesnot require a p-type substrate.

As shown in step 430 and in FIG. 4( c), the diblock copolymer 403 selfassembly process is performed on top of this oxide layer 402, and thenanometer-scale pattern is transferred into oxide 402 using the RIEprocess depicted earlier in FIG. 3( c).

After the RIE, the polymer 403 is stripped, and the wafer cleaned (e.g.,by O2 plasma, and wet chemical cleaner, or the like), thereby leaving aporous dielectric (oxide) film 402A on silicon 401, as shown in step 440and FIG. 4( d).

At this stage, the nanometer-scale holes 404 can be optionally shrunk(e.g., to any desired size after the holes are formed) using a nitridedeposition and anisotropic etch.

That is, as described above, one can start initially with differentpolymer molecular weights to set (e.g., template or define) any of thesize, the distribution and spacing of the holes of the polymer.

However, as another option, a fixed polymer could be used, and after thepolymer pattern has been transferred into oxide, the holes could bewidened or shrunk once they are in the dielectric material. There aretwo exemplary methods for performing such a widening or shrinking of theholes.

First, in FIG. 4( d) in which the PS has been transferred into the oxideto make them porous, the holes could be further etched (e.g.,overetched), which would widen the holes further laterally, but preservetheir center positions, center-to-center spacing, and uniformity. Thiswould make the holes larger. Alternatively, the holes could be shrunk bydepositing a conformal, very thin (e.g., having a size of ˜2-8 nm)nitride dielectric 28 deposition, and then performing an anisotropicsilicon nitride RIE etch, which leaves a small nitride ring around theedge of the hole, thereby making the hole narrower than before, butpreserving the uniformity of the size.

Thus, the size of the nanoparticles (to be built) can be suitablyadjusted by this step, and allows setting and precisely controlling thedimensions of the nanoparticles.

Hence, in contrast to the conventional techniques including CVDprocesses of making a nanocrystal gate device, in which all that can beset is an exemplary particle dimension “which may be within a range of2-50 nm” and which are scattered randomly all over the wafer with anaverage distance of “X”, the invention can achieve a very precisecontrolling of the dimensions of every particle, and can set a veryprecise specification (e.g., a specification can be made for “a particlehaving a 20 nm ±1-2 nm, and positioned such that each particles isspaced 40 nm from the next”).

Hence, a precise spacing and sizing can be obtained by the invention.Indeed, the invention has been shown to achieve a substantially uniformparticle spacing (e.g., a center-to-center spacing between adjacentparticles) of no more than 20%. More specifically, the invention hasbeen shown to achieve a substantially uniform particle spacing, having avariance of the spacing within a range of about 10 to 20%. This is incontrast to the CVD method in which the particles are typicallyclustered randomly on the wafer.

Next, as shown in step 450 and in FIG. 4( e), a program oxide 405 isthermally grown (e.g., having an exemplary thickness within a range ofabout 1.5 to about 4 nm).

This is followed by step 460 in which a conformal silicon 406 (e.g.,similar to the amorphous or polysilicon, etc. as above in step 350 ofFIG. 3( e)) is deposited, as shown in FIG. 4( f).

As shown in step 470 and in FIG. 4( g), nanocrystals 407 are defined andisolated from each other with an anisotropic silicon RIE which stopswhen the oxide layer below is reached.

The thermal oxide between the nanocrystals can be optionally thinned orremoved at this stage by selective wet chemical or RIE etching.

Next, in step 480 and as shown in FIG. 4( h), a layer of oxide 408 isdeposited over (e.g., on top of) the nanocrystals. This layer 408 willserve as the control oxide in the device (e.g., typical thickness valuesrange from about 4 to about 10 nm).

The control oxide is formed preferably by deposited low-temperatureoxide such as low pressure CVD (LPCVD) oxide (or plasma-en chanced CVD(PECVD) or rapid thermal CVD (RTCVD) or atomic layer deposition (ALD)).Alternatively, the control oxide may be formed by thermal oxidation(e.g., preferably at a temperature within a range of about 700° to about1100°) of the silicon nanocrystals. The gate material 409 is depositednext, and is preferably formed of poly-Si or metal having a suitablethickness.

The nanocrystals can optionally be crystallized using a high-temperatureanneal. It is noted that typically, the invention may use an amorphoussilicon layer which is deposited and then etched. Hence, typically thematerial is amorphous and not necessarily crystalline. However, theconventional device fabrication methods oftentimes use temperatureswhich 30 are high enough such that the particles become crystallized.Thus, with the invention, if the temperature was kept relatively low(the temperature range depending, of course, on the material beingused), then the amorphous nature of the material could be retained.

It is noted again that, while the exemplary embodiment above, has usedsilicon to generate the nanocrystals, the invention is not so limited.Indeed, any material could be used so long as the material can bedirectionally etched and can be conformally deposited. For example,instead of silicon, Ge, SiGe, or another material could be employed forthe nanocrystals.

Device Patterning:

Once the gate stack is grown, the device can be completed (source/drainpatterning, gate contact) using standard FET fabrication processes.

Such processes may involve removing the nanocrystals from thesource/drain region, patterning the source/drain, and performing aself-aligned source/drain implant to define highly-doped regions. Theseprocesses are schematically illustrated in step 490 and in FIG. 4( i).

Thus, with the unique and unobvious combination of exemplary features ofthe invention, a nanocrystal memory device can be formed in which thenanocrystals can be defined using a self-assembly process.

Further, the nanocrystal memory device (and method for forming it)allows good control over the uniformity of the size of the nanocrystalparticles, and over their distribution (e.g., where the nanocrystals arelocated 31 and the spacing between them). Thus, the inventive methodresults in a device having a regular array of such nanocrystalsthroughout the active area of the device.

While the invention has been described in terms of several exemplaryembodiments, those skilled in the art will recognize that the inventioncan be practiced with modification within the spirit and scope of theappended claims.

Further, it is noted that, Applicant's intent is to encompassequivalents of all claim elements, even if amended later duringprosecution.

1. A method of making a nanoparticle array, comprising: replicating adimension of a self-assembled film into a dielectric film, to form aporous dielectric film; conformally depositing a material over saidporous dielectric film; anisotropically and selectively etching saiddeposited material; and shrinking said nanoparticles by oxidation oretching.
 2. A method of making a nanoparticle array, comprising:replicating a dimension of a self-assembled film into a dielectric film,to form a porous dielectric film; conformally depositing a material oversaid porous dielectric film; anisotropically and selectively etchingsaid deposited material; and one of shrinking pores with a spacerprocess prior to forming said nanoparticles, and enlarging pores byetching prior to said forming said nanoparticles.
 3. A method of makinga nanoparticle array, comprising: replicating a dimension of aself-assembled film into a dielectric film, to form a porous dielectricfilm; conformally depositing a material over said porous dielectricfilm; anisotropically and selectively etching said deposited material tocreate the nanoparticle array; controlling a dimension of nanoparticlesin the nanoparticle array; and over-etching pores in the porousdielectric film to laterally widen the pores.
 4. A method of making ananoparticle array, comprising: replicating a dimension of aself-assembled film into a dielectric film, to form a porous dielectricfilm; conformally depositing a material over said porous dielectricfilm; anisotropically and selectively etching said deposited material tocreate the nanoparticle array; controlling a dimension of nanopailiclesin the nanoparticle array; and shrinking a size of pores in the porousdielectric film, said shrinking comprising: depositing a conformalnitride dielectric material; and performing an anisotropic siliconnitride etch.
 5. A method of making a nanoparticle array, comprising:replicating a dimension of a self-assembled film into a dielectric film,to form a porous dielectric film; conformally depositing a material oversaid porous dielectric film; anisotropically and selectively etchingsaid deposited material to create the nanoparticle array; andcontrolling a dimension of nanoparticles in the nanoparticle array,wherein a spacing of said nanoparticles comprises a variance of no morethan 20%.
 6. A method of making a nanoparticle array, comprising:replicating a dimension of a self-assembled film into a dielectric film,to form a porous dielectric film; conformally depositing a material oversaid porous dielectric film; anisotropically and selectively etchingsaid deposited material to create the nanoparticle array; andcontrolling a dimension of nanoparticles in the nanoparticle array,wherein a center-to-center spacing between adjacent nanoparticles iscontrolled to comprise a variance within a range of 10% to about 20%. 7.A method of making a nanoparticle array, comprising: replicating adimension of a self-assembled film into a dielectric film, to form aporous dielectric film; conformally depositing a material over saidporous dielectric film; anisotropically and selectively etching saiddeposited material to create the nanoparticle array; and shrinking asize of pores in the porous dielectric film, said shrinking comprising:depositing a conformal nitride dielectric material; and performing ananisotropic silicon nitride etch.